Oscillatory transenantiomerization of the selected 2-arylpropionic acids (2-APAs) in vitro as a spontaneous phenomenon

Abstract

In this paper, we summarize the results of our earlier investigations on an attempted enantioseparation of the selected 2-arylpropionic acids (2-APAs) by means of the chiral thin layer chromatography (TLC). These results have been originally presented in a series of the research papers published in several chromatography journals. In the current article it was reminded that the prolonged storage of the investigated 2-APAs in the aqueous and the non-aqueous solutions results in an oscillatory change of the respective retardation factor (RF) and the specific rotation ([Æ]D) values. An assumption is introduced as to the chemical nature of the observed phenomenon. It is assumed that the observed oscillations are due to the repeated structural inversion (in our study labelled as oscillatory transenantiomerization) of one enantiomer to its respective antimer. One attempts to at least roughly explain the molecular mechanism of transenantiomerization either by keto-enol tautomerism, or by formation of an intermediate enolic anion, any of these two reaction mechanisms possible only in the basic environment. Then one reflects on the most probable mechanism responsible for the oscillatory nature of the observed structural inversion. It is concluded that the oscillations could be due to an enhanced viscosity of the investigated 2-APA solutions (as compared with those of the respective pure solvents) and/or due to the molecular self-organization within these solutions, resulting in anisotropic properties thereof. Finally, it is concluded that an ultimate explanation of the observed oscillatory transenantiomerization of the selected 2-APAs could probably be offered by the Brusselator-type kinetic model implemented with the diffusion term. In the last section of this paper, argumentation is presented strongly in favour of this particular model and against any alternative speculation as to the supramolecular nature of the observed oscillatory phenomena.